Desulfurization and novel compositions for same

ABSTRACT

A composition comprising an iron oxide and a promoter, wherein at least a portion of the promoter is present as a reduced valence promoter and methods of preparing such composition are disclosed. The thus-obtained composition is employed in a desulfurization zone to remove sulfur from a hydrocarbon stream.

FIELD OF THE INVENTION

[0001] This invention relates to the removal of sulfur from hydrocarbonstreams. In another aspect, this invention relates to compositionssuitable for use in the desulfurization of fluid streams of crackedgasolines and diesel fuels. A further aspect of this invention relatesto processes for the production of compositions for use in the removalof sulfur bodies from fluid streams of cracked gasolines and dieselfuels.

BACKGROUND OF THE INVENTION

[0002] The need for cleaner burning fuels has resulted in a continuingworld-wide effort to reduce sulfur levels in hydrocarbon streams such asgasoline and diesel fuels. The reduction of sulfur in such hydrocarbonstreams is considered to be a means for improving air quality because ofthe negative impact the sulfur has on performance of sulfur sensitiveitems such as automotive catalytic converters. The presence of oxides ofsulfur in automotive engine exhaust inhibits and may irreversibly poisonnoble metal catalysts in the converter. Emissions from an inefficient orpoisoned converter contain levels of non-combusted, non-methanehydrocarbons, oxides of nitrogen, and carbon monoxide. Such emissionsare catalyzed by sunlight to form ground level ozone, more commonlyreferred to as smog.

[0003] Thermally processed gasolines such as, for example, thermallycracked gasoline, visbreaker gasoline, coker gasoline and catalyticallycracked gasoline (hereinafter collectively referred to as “crackedgasoline”) contain, in part, olefins, aromatics, sulfur, and sulfurcontaining compounds. Since most gasolines, such as, automobilegasolines, racing gasolines, aviation gasolines, boat gasolines, and thelike contain a blend of, at least in part, cracked gasoline, reductionof sulfur in cracked gasoline will inherently serve to reduce the sulfurlevels in most gasolines, such as, for example, automobile gasolines,racing gasolines, aviation gasolines, boat gasolines, and the like.

[0004] The public discussion about gasoline sulfur has not centered onwhether or not sulfur levels should be reduced. A consensus has emergedthat lower sulfur gasoline reduces automotive emissions and improves airquality. Thus, the rules to date have focused on the required level ofreduction, the geographical areas in need of lower sulfur gasoline, andthe time frame for implementation.

[0005] As the concern over the impact of automotive air pollutioncontinues, it is clear that further effort to reduce the sulfur level inautomotive fuels will be required. While the current gasoline productscontain about 330 parts per million (ppm) sulfur, the US EnvironmentalProtection Agency recently issued regulations requiring the averagesulfur content in gasoline to be less than 30 ppm average with an 80 ppmcap. By 2008, the standards will effectively require every blend ofgasoline sold in the United States to meet the 30 ppm level.

[0006] In addition to the need to be able to produce low sulfur contentautomotive fuels, there is also a need for a process which will have aminimal effect on the olefin content of such fuels so as to maintain theoctane number (both research and motor octane number). Such a processwould be desirable since saturation of olefins greatly affects theoctane number. Such adverse effect on the olefin content is generallydue to the severe conditions normally employed, such as duringhydrodesulfurization, to remove thiophenic compounds (such as, forexample, thiophenes, benzothiophenes, alkyl thiophenes,alkylbenzothiophenes, alkyl dibenzothiophenes and the like) which aresome of the most difficult sulfur containing compounds to remove fromcracked gasoline. In addition, there is a need to avoid a system whereinthe conditions are such that the aromatic content of the crackedgasoline is lost through saturation. Thus, there is a need for a processwhich achieves desulfurization and maintains the octane number.

[0007] In addition to the need for removal of sulfur from crackedgasolines, there is a need for the petroleum industry to reduce thesulfur content in diesel fuels. In removing sulfur from diesel fuels byhydrodesulfurization, the cetane is improved but there is a large costin hydrogen consumption. Such hydrogen is consumed by bothhydrodesulfurization and aromatic hydrogenation reaction.

[0008] Thus, there is a need for a desulfurization process without asignificant consumption of hydrogen so as to provide a more economicalprocess for the treatment of cracked gasolines and diesel fuels.

[0009] As a result of the lack of success in providing a successful andeconomically feasible process for the reduction of sulfur levels incracked gasolines and diesel fuels, it is apparent that there is a needfor a better process for the desulfurization of such hydrocarbon streamswhich has minimal effect on octane levels while achieving high levels ofsulfur removal.

[0010] Traditionally, compositions used in processes for the removal ofsulfur from hydrocarbon streams have been agglomerates used in fixed bedapplications. Because of the various process advantages of fluidizedbeds, hydrocarbon streams are sometimes processed in fluidized bedreactors. Fluidized bed reactors have advantages over fixed bedreactors, such as, for example, better heat transfer and better pressuredrop. Fluidized bed reactors generally use reactants that areparticulate. The size of these particulates is generally in the range offrom about 1 micron to about 1000 microns. However, the reactants usedgenerally do not have sufficient attrition resistance for allapplications. Consequently, finding a composition with sufficientattrition resistance that removes sulfur from these hydrocarbon streamsand that can be used in fluidized, transport, moving, or fixed bedreactors is desirable and would be a significant contribution to the artand to the economy.

SUMMARY OF THE INVENTION

[0011] It is thus an object of the present invention to provide novelcompositions that can be used for the removal of sulfur from hydrocarbonstreams.

[0012] Another object of the present invention is to provide processesfor the production of novel compositions which are usable in thedesulfurization of hydrocarbon streams.

[0013] Another object of the present invention is to provide a processfor the removal of sulfur from hydrocarbon streams which minimizes theconsumption of hydrogen and the saturation of olefins and aromaticscontained in such streams.

[0014] A still further object of the present invention is to provide adesulfurized cracked gasoline that contains less than about 100 ppm,preferably less than 50 ppm, of sulfur based on the weight of thedesulfurized cracked gasoline, and which contains essentially the sameamount of olefins and aromatics as are in the cracked gasoline fromwhich such desulfurized cracked gasoline was made.

[0015] The first embodiment of this invention includes a novelcomposition suitable for use in desulfurizing hydrocarbons. The novelcomposition can comprise:

[0016] a) an iron oxide; and

[0017] b) a promoter wherein at least a portion of the promoter ispresent as a reduced valence promoter.

[0018] The invention further includes a second embodiment with anothernovel composition suitable for use in desulfurizing hydrocarbons. Thenovel composition comprises: a) an iron oxide; b) a silicon-containingmaterial; c) an aluminum-containing material selected from the groupconsisting of alumina, aluminate and combinations thereof; and d) apromoter wherein at least a portion of the promoter is present as areduced valence promoter.

[0019] The third embodiment of this invention includes a novel processfor the production of the inventive composition comprising:

[0020] a) admixing: 1) a liquid, 2) an iron-containing compound, 3) asilicon-containing material, 4) alumina, and 5) a promoter so as to forma mixture thereof;

[0021] b) drying the mixture so as to form a dried mixture;

[0022] c) calcining the dried mixture so as to form a calcined mixture;

[0023] d) reducing the calcined mixture with a suitable reducing agentunder suitable conditions to produce a composition having a reducedvalence promoter content therein, and

[0024] e) recovering the composition.

[0025] The fourth embodiment of this invention includes another novelprocess for the production of the inventive composition comprising:

[0026] a) admixing: 1) a liquid, 2) an iron-containing compound, 3) asilicon-containing material, and 4) alumina so as to form a mixturethereof;

[0027] b) drying the mixture so as to form a dried mixture;

[0028] c) calcining the dried mixture so as to form a calcined mixture;

[0029] d) incorporating a promoter onto or into the calcined mixture soas to form a promoted mixture;

[0030] e) drying the promoted mixture so as to form a dried promotedmixture;

[0031] f) calcining the dried promoted mixture so as to form a calcinedpromoted mixture;

[0032] g) reducing the calcined promoted mixture with a suitablereducing agent under suitable conditions to produce a composition havinga reduced valence promoter content therein; and

[0033] h) recovering the composition.

[0034] The fifth embodiment of this invention includes a process for theremoval of sulfur from a hydrocarbon stream comprising:

[0035] a) contacting the hydrocarbon stream with a compositioncomprising an iron oxide and a promoter wherein at least a portion ofthe promoter is present as a reduced valence promoter in an amount whichwill effect the removal of sulfur from the hydrocarbon stream in adesulfurization zone under conditions such that there is formed adesulfurized hydrocarbon stream and a sulfurized composition;

[0036] b) separating the desulfurized hydrocarbon stream from thesulfurized composition thereby forming a separated desulfurizedhydrocarbon stream and a separated sulfurized composition;

[0037] c) regenerating at least a portion of the separated sulfurizedcomposition in a regeneration zone so as to remove at least a portion ofthe sulfur contained therein and/or thereon thereby forming aregenerated composition;

[0038] d) reducing the regenerated composition in a reduction zone so asto provide a reduced composition having a reduced valence promotercontent therein which will effect the removal of sulfur from ahydrocarbon stream when contacted with same; and thereafter

[0039] e) returning at least a portion of the reduced composition to thedesulfurization zone.

[0040] In step (a), the composition can also comprise, consist of, orconsist essentially of an iron oxide, a silicon-containing material, analuminum-containing material selected from the group consisting ofalumina, aluminate and combinations thereof, and a promoter wherein atleast a portion of the promoter is present as a reduced valence promoterin an amount which will effect the removal of sulfur from thehydrocarbon stream in a desulfurization zone under conditions such thatthere is formed a desulfurized hydrocarbon stream and a sulfurizedcomposition.

[0041] Other aspects, objectives, and advantages of the presentinvention will be apparent from the detailed description of theinvention and the appended claims.

DETAILED DESCRIPTION OF THE INVENTION

[0042] The term “gasoline” denotes a mixture of hydrocarbons boiling inthe range of from about 100° F. to about 500° F., or any fractionthereof. Examples of suitable gasoline include, but are not limited to,hydrocarbon streams in refineries such as naphtha, straight run naphtha,coker naphtha, catalytic gasoline, visbreaker naphtha, alkylate,isomerate, reformate, and the like and combinations thereof.

[0043] The term “cracked gasoline” denotes a mixture of hydrocarbonsboiling in the range of from about 100° F. to about 500° F., or anyfraction thereof, that are products from either thermal or catalyticprocesses that crack larger hydrocarbon molecules into smallermolecules. Examples of suitable thermal processes include, but are notlimited to, coking, thermal cracking, visbreaking, and the like andcombinations thereof. Examples of suitable catalytic cracking processesinclude, but are not limited to, fluid catalytic cracking, heavy oilcracking, and the like and combinations thereof. Thus, examples ofsuitable cracked gasoline include, but are not limited to, cokergasoline, thermally cracked gasoline, visbreaker gasoline, fluidcatalytically cracked gasoline, heavy oil cracked gasoline, and the likeand combinations thereof. In some instances, the cracked gasoline may befractionated and/or hydrotreated prior to desulfurization when used as ahydrocarbon stream in the process of the present invention.

[0044] The term “diesel fuel” denotes a mixture of hydrocarbons boilingin the range of from about 300° F. to about 750° F., or any fractionthereof. Examples of suitable diesel fuels include, but are not limitedto, light cycle oil, kerosene, jet fuel, straight-run diesel,hydrotreated diesel, and the like and combinations thereof.

[0045] The term “sulfur” denotes sulfur in any form such as elementalsulfur or a sulfur compound normally present in a hydrocarbon-containingfluid such as cracked gasoline or diesel fuel. Examples of sulfur whichcan be present during a process of the present invention usuallycontained in a hydrocarbon stream, include, but are not limited to,hydrogen sulfide, carbonyl sulfide (COS), carbon disulfide (CS₂),mercaptans (RSH), organic sulfides (R—S—R), organic disulfides(R—S—S—R), thiophenes, substituted thiophenes, organic trisulfides,organic tetrasulfides, benzothiophenes, alkyl thiophenes, alkylbenzothiophenes, alkyl dibenzothiophenes, and the like and combinationsthereof as well as the heavier molecular weights of same which arenormally present in a diesel fuel of the types contemplated for use in aprocess of the present invention, wherein each R can be an alkyl orcycloalkyl or aryl group containing one carbon atom to ten carbon atoms.

[0046] The term “fluid” denotes gas, liquid, vapor, and combinationsthereof.

[0047] The term “gaseous” denotes that state in which thehydrocarbon-containing fluid, such as cracked-gasoline or diesel fuel,is primarily in a gas or vapor phase.

[0048] In accordance with the first embodiment of the present invention,the inventive composition comprises, consists of, or consistsessentially of an iron oxide and a promoter.

[0049] The term “iron oxide”, as used herein, denotes any oxide of iron,including but not limited to ferric oxide (Fe₂O₃), ferrous oxide (FeO),and ferroso-ferric oxide (Fe₃O₄).

[0050] The iron oxide will preferably be present in the inventivecomposition in an amount in the range of from about 10 to about 90weight percent iron oxide, more preferably in an amount in the range offrom about 30 to about 80 weight percent iron oxide, and most preferablyin an amount in the range of from about 40 to about 70 weight percentiron oxide based on the total weight of the inventive composition.

[0051] The term “promoter” denotes any component, which when added tothe composition of the present invention, helps promote thedesulfurization of hydrocarbon streams. Such promoters can be at leastone metal, metal oxide, precursor for the metal oxide, solid solution ofmore than one metal, or alloy of more than one metal wherein the metalcomponent is selected from the group consisting of nickel, cobalt, iron,manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony,vanadium, gold, platinum, ruthenium, iridium, chromium, palladium,titanium, zirconium, rhodium, rhenium, and combinations of any two ormore thereof.

[0052] Some examples of promoter metal containing compounds includemetal acetates, metal carbonates, metal nitrates, metal sulfates, metalthiocyanates, and the like and combinations thereof. Preferably, themetal of the promoter is selected from the group consisting of nickel,iron, and combinations there.

[0053] The inventive composition having a reduced valence promotercontent is a composition that has the ability to react chemically and/orphysically with sulfur. It is also preferable that the inventivecomposition removes diolefins and other gum forming compounds fromcracked gasoline.

[0054] The term “metal” denotes metal in any form such as elementalmetal or a metal-containing compound.

[0055] The term “metal oxide” denotes metal oxide in any form such as ametal oxide or a metal oxide precursor.

[0056] During the preparation of a composition of the present invention,the promoter selected from the group consisting of metals, metal oxides,and the like and combinations thereof may initially be in the form of ametal-containing compound and/or a metal oxide precursor. It should beunderstood that when the promoter is initially a metal-containingcompound and/or a metal oxide precursor, a portion of, or all of, suchcompound and/or precursor may be converted to the corresponding metal ormetal oxide of such compound and/or precursor during the inventiveprocess disclosed herein.

[0057] Typically, the common oxidation state of the promoter is combinedwith the iron oxide portion of the inventive composition. The number ofoxygen atoms associated with the promoter must be reduced to form areduced valence promoter. Consequently, at least a portion of thepromoter present in the inventive composition must be present as areduced valence promoter. While not wishing to be bound by theory, it isbelieved that the reduced valence promoter can chemisorb, cleave, orremove sulfur. Thus, either the number of oxygen atoms associated withthe promoter is reduced or the oxidation state of the promoter is azero-valent metal. For example, if nickel is the promoter metal, nickeloxide (NiO) can be used and the reduced valence nickel (promoter metal)can be either nickel metal (Ni⁰) or a non-stoichiometric nickel oxidehaving a formula of NiO_((1-x)) wherein 0<x<1. If tungsten is thepromoter, tungsten oxide (WO₃) can be used and the reduced valencetungsten (promoter metal) can be either tungsten oxide (WO₃), tungstenmetal (W⁰), or a non-stoichiometric tungsten oxide having a formula ofWO_((3-y)) wherein 0<y<3.

[0058] Preferably, the promoter is present in an amount which willeffect the removal of sulfur from the hydrocarbon stream when contactedwith the inventive composition under desulfurization conditions. Of thetotal quantity of the promoter present in the inventive composition, itis preferred for at least about 10 weight percent of the promoter to bepresent in the form of a reduced valence promoter, more preferably atleast about 40 weight percent of the promoter is a reduced valencepromoter, and most preferably at least 80 weight percent of the promoteris a reduced valence promoter for best activity in sulfur removal. Thereduced valence promoter will generally be present in the inventivecomposition in an amount in the range of from about 1 to about 60 weightpercent reduced valence promoter based on the total weight of theinventive composition, preferably in an amount in the range of fromabout 5 to about 40 weight percent reduced valence promoter, and mostpreferably in an amount in the range of from 8 to 20 weight percentreduced valence promoter for best activity in sulfur removal. When thepromoter comprises a bimetallic promoter, the bimetallic promoter shouldcomprise a ratio of the two metals forming such bimetallic promoter inthe range of from about 20:1 to about 1:20.

[0059] In accordance with the second embodiment of the present inventionthe inventive composition can also comprise, consist of, or consistessentially of an iron oxide, an aluminum-containing material selectedfrom the group consisting of alumina, aluminate, and combinationsthereof, a silicon-containing material, and a promoter.

[0060] The disclosure included with the first embodiment regarding aniron oxide and a promoter and the weight percents of same areincorporated hereto and apply equally to the inventive composition ofthis second embodiment.

[0061] The silicon-containing material used in the preparation of, andpresent in the inventive compositions may be either in the form ofsilica or in the form of one or more silicon-containing materials.

[0062] Any suitable silicon-containing material may be employed in thecomposition such as, for example, diatomite, expanded perlite,silicalite, silica colloid, flame-hydrolized silica, silica gel,precipitated silica, and the like, and combinations thereof. Inaddition, silicon compounds that are convertible to silica such assilicic acid, ammonium silicate, and the like, and combinations thereofcan also be employed.

[0063] More preferably the silicon-containing material is in the form ofexpanded perlite. The term “perlite” as used herein is the petrographicterm for a siliceous volcanic rock, which naturally occurs in certainregions throughout the world. The distinguishing feature, which sets itapart from other volcanic minerals, is its ability to expand four totwenty times its original volume when heated to certain temperatures.When heated above 1600° F., crushed perlite expands due to the presenceof combined water with the crude perlite rock. The combined watervaporizes during the heating process and creates countless tiny bubblesin the heat softened glassy particles. The glass sealed bubbles accountfor its light weight. Expanded perlite can be manufactured to weigh aslittle as 2.5 lbs per cubic foot.

[0064] The typical elemental analysis of expanded perlite is: silicon33.8%, aluminum 7%, potassium 3.5%, sodium 3.4%, calcium 0.6%, magnesium0.2%, iron 0.6%, trace elements 0.2%, oxygen (by difference) 47.5%, andbound water 3%.

[0065] Typical physical properties of expanded perlite are: softeningpoint 1600-2000° F., fusion point 2300-2450° F., pH 6.6-6.8, andspecific gravity 2.2-2.4.

[0066] The term “particulate expanded perlite” or “milled expandedperlite” as used herein denotes that form of expanded perlite which hasbeen subjected to crushing so as to form a particulate mass wherein theparticle size of such mass is comprised of at least 97% of particleshaving a size of less than 2 microns.

[0067] The inventive composition contains an aluminum-containingmaterial selected from the group consisting of alumina, aluminate, andcombinations thereof. Alumina can be used to produce the composition.The alumina employed in the preparation of the composition can be anysuitable commercially available aluminum-containing substance including,but not limited to, aluminum chlorides, aluminum nitrates, colloidalalumina solutions, hydrated aluminas, peptized aluminas, and, generally,those alumina compounds produced by the dehydration of alumina hydrates.The preferred alumina is hydrated alumina such as, for example, bohemiteor pseudobohemite for best activity and sulfur removal. When thecomposition is exposed to high temperatures (e.g., during calcinations)at least a portion, preferably a substantial portion of the alumina canbe converted to an aluminate.

[0068] The aluminum-containing material will preferably be present inthe inventive composition in an amount in the range of from about 1.0 toabout 30 weight percent, preferably in an amount in the range of fromabout 5 to about 25 weight percent, and most preferably, in the range offrom 10 to 22 weight percent, based on the total weight of the inventivecomposition.

[0069] The silicon-containing material will preferably be present in theinventive composition in an amount in the range of from about 10 toabout 40 weight percent silicon-containing material based on the totalweight of the inventive composition, more preferably in an amount in therange of from about 12 to about 35 weight percent, and most preferablyin the range of from 15 to 30 weight percent.

[0070] The inventive composition can be a particulate in the form of oneof granules, extrudates, tablets, spheres, pellets, or microspheres.Preferably, the particulate is a microsphere.

[0071] In accordance with the third embodiment of the present invention,the inventive composition(s) can be produced by the following inventiveprocess.

[0072] In the production of an inventive composition, the compositioncan generally be prepared by admixing a liquid, an iron-containingcompound, a silicon-containing material, alumina, and a promoter inappropriate proportions by any suitable method or manner which providesfor the intimate mixing of such components to thereby provide asubstantially homogenous mixture thereof comprising a liquid, aniron-containing compound, a silicon-containing material, alumina, and apromoter. The term “admixing,” as used herein, denotes mixing componentsin any order and/or any combination or sub-combination. Any suitablemeans for admixing the components of the inventive composition can beused to achieve the desired dispersion of such components. Examples ofsuitable admixing include, but are not limited to, mixing tumblers,stationary shelves or troughs, Eurostar mixers, which are of the batchor continuous type, impact mixers, and the like. It is presentlypreferred to use a Eurostar mixer in the admixing of the components ofthe inventive composition.

[0073] The liquid can be any solvent capable of dispersing aniron-containing compound, a silicon-containing material, alumina, and apromoter, and, preferably, the liquid can be selected from the groupconsisting of water, ethanol, acetone and combinations of any two ormore thereof. Most preferably, the liquid is water.

[0074] The iron-containing compound used in the preparation of acomposition of the present invention can either be in the form of aniron oxide or in the form of one or more iron compounds that areconvertible to an iron oxide under the conditions of preparationdescribed herein. Examples of suitable iron compounds include, but arenot limited to, iron sulfides, iron sulfates, iron hydroxides, ironcarbonates, iron acetates, iron nitrates, and the like and combinationsthereof. Preferably, the iron-containing compound is in the form of apowdered iron oxide.

[0075] As stated above, the starting alumina component of thecomposition can be any suitable commercially availablealuminum-containing substance including, but not limited to, aluminumchlorides, aluminum nitrates, colloidal alumina solutions and,generally, those alumina compounds produced by the dehydration ofalumina hydrates.

[0076] The components of the inventive composition are mixed to providea mixture which can be in the form selected from the group consisting ofa wet mix, dough, paste, slurry and the like. Such mixture can then beshaped to form a particulate selected from the group consisting of agranule, an extrudate, a tablet, a sphere, a pellet, or a microsphere.For example, if the resulting mixture is in the form of a wet mix, thewet mix can be densified, dried under a drying condition as disclosedhereinafter, calcined under a calcining condition as disclosedhereinafter, and thereafter shaped, or particulated, through thegranulation of the densified, dried, calcined mix to form granulates.Also, for example, when the mixture of the components results in a formof the mixture which is either in a dough state, or a paste state, suchmixture can then be shaped, preferably extruded to form a particulate.The resulting particulates are then dried under a drying condition asdisclosed hereinafter and then calcined under a calcining condition asdisclosed hereinafter. More preferably, when the mix is in the form of aslurry, the particulation of such slurry is achieved by spray drying theslurry to form microspheres thereof having a size of about 500 or lessmicrons. Such microspheres are then subjected to drying under a dryingcondition as disclosed hereinafter and are then calcined under acalcining condition as disclosed hereinafter.

[0077] When the particulation is achieved by preferably spray drying, adispersant component can optionally be utilized and can be any suitablecompound that helps to promote the spray drying ability of the mix whichis preferably in the form of a slurry. In particular, these componentsare useful in preventing deposition, precipitation, settling,agglomerating, adhering, and caking of solid particles in a fluidmedium. Suitable dispersants include, but are not limited to, condensedphosphates, sulfonated polymers, and combinations thereof. The term“condensed phosphates” refers to any dehydrated phosphate containingmore than one phosphorus atom and having a phosphorus-oxygen-phosphorusbond. Specific examples of suitable dispersants include sodiumpyrophosphate, sodium metaphosphate, sulfonated styrene maleic anhydridepolymer, and combinations thereof. The amount of dispersant componentused is generally in the range of from about 0.01 weight percent basedon the total weight of the components to about 10 weight percent.Preferably, the amount of the dispersant component used is generally inthe range of from about 0.1 weight percent to about 8 weight percent.

[0078] In preparing the preferred spray dried composition, an acidcomponent can be used. In general, the acid component can be an organicacid or a mineral acid such as nitric acid. If the acid component is anorganic acid, it is preferred to be a carboxylic acid. If the acidcomponent is a mineral acid, it is preferred to be a nitric acid or aphosphoric acid. Mixtures of these acids can also be used. Generally,the acid is used with water to form a dilute aqueous acid solution. Theamount of acid in the acid component is generally in the range of fromabout 0.01 volume percent based on the total volume of the acidcomponent to about 20 volume percent.

[0079] Generally, the spray dried mixture has a mean particle size inthe range of from about 10 micrometers to about 1000 micrometers,preferably in the range of from about 20 micrometers to from about 150micrometers.

[0080] The term “mean particle size” refers to the size of theparticulate material as determined by using a RO-TAP® Testing SieveShaker, manufactured by W. S. Tyler Inc., of Mentor, Ohio, or othercomparable sieves. The material to be measured is placed in the top of anest of standard 8-inch diameter stainless steel framed sieves with apan on the bottom. The material undergoes sifting for a period of about10 minutes; thereafter, the material retained on each sieve is weighed.The percent retained on each sieve is calculated by dividing the weightof the material retained on a particular sieve by the weight of theoriginal sample. This information is used to compute the mean particlesize.

[0081] The mixture is dried to form a dried mixture. The dryingconditions, as referred to herein, can include a temperature in therange of from about 150° F. to about 450° F., preferably in the range offrom about 190° F. to about 410° F. and, most preferably, in the rangeof from 200° F. to 350° F. Such drying conditions can also include atime period generally in the range of from about 0.5 hour to about 60hours, preferably in the range of from about 1 hour to about 40 hours,and most preferably, in the range of from 1.5 hours to 20 hours. Suchdrying conditions can also include a pressure generally in the range offrom about atmospheric (i.e., about 14.7 pounds per square inchabsolute) to about 150 pounds per square inch absolute (psia),preferably in the range of from about atmospheric to about 100 psia and,most preferably about atmospheric, so long as the desired temperaturecan be maintained. Any drying method(s) known to one skilled in the artsuch as, for example, air drying, heat drying, and the like andcombinations thereof can be used. Preferably, heat drying is used.

[0082] The dried mixture is then calcined to form a calcined mixture.Preferably, the dried mixture is calcined in an oxidizing atmospheresuch as in the presence of oxygen or air. The calcining conditions, asreferred to herein, can include a temperature in the range of from about400° F. to about 1500° F., preferably in the range of from about 800° F.to about 1500° F. and, more preferably, in the range of from 900° F. to1400° F. Such calcining conditions can also include a pressure,generally in the range of from about 7 psia to about 750 psia,preferably in the range of from about 7 psia to about 450 psia and, mostpreferably, in the range of from 7 psia to 150 psia, and a time periodin the range of from about 1 hour to about 60 hours, preferably for atime period in the range of from about 1 hour to about 20 hours and,most preferably, for a time period in the range of from 1 hour to 15hours. In the process of this invention, the calcination can convert atleast a portion of the alumina to aluminate.

[0083] The calcined mixture is thereafter subjected to reduction with asuitable reducing agent, preferably hydrogen, so as to produce acomposition having a substantially reduced valence promoter contenttherein, preferably a substantially zero-valent promoter contenttherein, with such zero-valent promoter being present in an amountsufficient to permit the removal of sulfur from a hydrocarbon streamsuch as cracked gasoline or diesel fuel, according to the processdisclosed herein.

[0084] The reduction conditions can include a temperature in the rangeof from about 100° F. to about 1500° F., a pressure in the range of fromabout 15 psia to about 1500 psia and for a time sufficient to permit theformation of a reduced valence promoter.

[0085] The composition is then recovered.

[0086] In accordance with the fourth embodiment of the presentinvention, the inventive composition(s) can also be produced by thefollowing inventive process.

[0087] In the production of an inventive composition of the presentinvention, the composition can generally be prepared by admixing aliquid, an iron-containing compound, a silicon-containing material, andalumina in appropriate proportions by any suitable methods or mannerwhich provides for the intimate mixing of such components to therebyprovide a substantially homogenous mixture comprising a liquid (asdescribed above), an iron-containing compound, a silicon-containingmaterial, and alumina. Any suitable means for admixing these components,as described above, can be used to achieve the desired dispersant ofsuch components.

[0088] The components are mixed to provide a mixture which can be in theform selected from the group consisting of a wet mix, dough, paste,slurry, and the like. Such mixture can then optionally be shaped bydensifying, extruding, or spray drying to form a particulate selectedfrom the group consisting of a granule, an extrudate, a tablet, asphere, a pellet, or a microsphere, as described above.

[0089] The mixture is then dried to form a dried mixture, according tothe drying conditions described above.

[0090] The dried mixture is then calcined to form a calcined mixtureaccording to the calcining conditions described above. This calciningstep can convert at least a portion of the alumina to aluminate.

[0091] The calcined mixture comprising an iron-containing compound, asilicon-containing material, and alumina (or aluminate), is thenincorporated with a promoter. The promoter can be incorporated into oronto the calcined mixture by any suitable means or method known in theart for incorporating a promoter into or onto a substrate material.

[0092] A preferred method of incorporating is to impregnate using anystandard incipient wetness impregnation technique (i.e. essentiallycompletely or partially filling the pores of a substrate material with asolution of the incorporating elements) for impregnating a substrate.This preferred method uses an impregnating solution comprising thedesirable concentration of a promoter so as to ultimately provide apromoted mixture that can then be subjected to drying and calciningfollowed by reduction with a reducing agent such as hydrogen.

[0093] A preferred impregnating solution comprises a solution formed bydissolving a metal containing compound, preferably such metal containingcompound is in the form of a metal salt such as a metal chloride, ametal nitrate, a metal sulfate, and he like and combinations thereof, ina solvent such as water, alcohols, esters, ethers, ketones, andcombinations thereof. The concentration of the metal promoter in thesolution can be in the range of from about 0.1 gram of metal promoterper gram of solution to about 16.6 grams of metal promoter per 100 gramsof solution. Preferably, the weight ratio of metal promoter to thesolvent of such solution can be in the range of from about 1:1 to about4:1 but, more preferably it is in the range of from 1.5:1 to 3:1. It ispreferred for the particulates to be impregnated with a nickel componentby use of a solution containing nickel nitrate hexahydrate dissolved inwater.

[0094] Following the incorporating of the calcined mixture, preferablyby impregnation, with a promoter, the resulting promoted mixture is thensubjected to drying under drying conditions, as described above, andcalcined under calcining conditions, as described above, to form acalcined promoted mixture. The calcined promoted mixture can then besubjected to reduction with a reducing agent, as described above, tothereby provide an inventive composition. The composition can then berecovered.

[0095] In preparing the composition, a promoter can be added as acomponent of the original mixture, as in the third embodiment, or it canbe added after the original mixture has been spray dried and calcined,as in the fourth embodiment. If a promoter is added after the mixturehas been dried and calcined, the promoted mixture should be dried andcalcined a second time. The promoted mixture is preferably dried asecond time at a temperature generally in the range of from about 100°F. to about 650° F. Preferably, the promoted mixture can be dried asecond time at a temperature generally in the range of from about 150°F. to about 600° F. and, more preferably, in the range of from 200° F.to 550° F. The time period for conducting the drying the second time isgenerally in the range of from about 0.5 hour to about 8 hours,preferably in the range of from about 1 hour to about 6 hours, and morepreferably in the range of from 1.5 hours to 4 hours. Such drying asecond time is generally carried out at a pressure in the range of fromabout atmospheric (i.e. about 14.7 psia) to about 100 psia, preferablyabout atmospheric. This dried promoted mixture is then calcined,preferably in an oxidizing atmosphere such as in the presence of oxygenor air, under calcining conditions, as described above.

[0096] The fifth embodiment of this invention includes a novel processfor the removal of sulfur from a hydrocarbon stream. This processcomprises:

[0097] a) contacting the hydrocarbon stream with a composition of thefirst, second, third or fourth embodiment of the present invention in adesulfurization zone under conditions such that there is formed adesulfurized hydrocarbon stream and a sulfurized composition;

[0098] b) separating the desulfurized hydrocarbon stream from thesulfurized composition thereby forming a separated desulfurizedhydrocarbon stream and a separated sulfurized composition;

[0099] c) regenerating at least a portion of the separated sulfurizedcomposition in a regeneration zone so as to remove at least a portion ofthe sulfur contained therein and/or thereon thereby forming aregenerated composition;

[0100] d) reducing the regenerated composition in a reduction zone so asto provide a reduced composition having a reduced valence promotercontent therein which will effect the removal of sulfur from ahydrocarbon stream when contacted with same; and thereafter

[0101] e) returning at least a portion of the reduced composition to thedesulfurization zone.

[0102] The contacting, in step a), of the hydrocarbon stream with theinventive composition in the desulfurization zone can be by any methodknown to those skilled in the art.

[0103] The desulfurization zone can be any zone wherein desulfurizationof a hydrocarbon stream can take place. Examples of suitable zones arefixed bed reactors, moving bed reactors, fluidized bed reactors,transport reactors, and the like. Presently a fluidized bed reactor or afixed bed reactor is preferred.

[0104] The desulfurization zone of step a) includes the followingconditions: total pressure, temperature, weight hourly space velocity,and hydrogen flow. These conditions are such that the inventivecomposition can desulfurize the hydrocarbon stream to produce adesulfurized hydrocarbon stream and a sulfurized composition.

[0105] The total pressure can be in the range of from about 15 poundsper square inch absolute (psia) to about 1500 psia. However, it ispresently preferred that the total pressure be in a range of from about50 psia to about 500 psia.

[0106] In general, the temperature should be sufficient to keep thehydrocarbon stream in essentially a vapor or gas phase. While suchtemperatures can be in the range of from about 100° F. to about 1000°F., it is presently preferred that the temperature be in the range offrom about 400° F. to about 800° F. when treating a cracked-gasoline,and in the range of from about 500° F. to about 900° F. when treating adiesel fuel.

[0107] Weight hourly space velocity (“WHSV”) is defined as the numericalratio of the rate at which a hydrocarbon stream is charged to thedesulfurization zone in pounds per hour at standard conditions attemperature and pressure (STP) divided by the pounds of compositioncontained in the desulfurization zone to which the hydrocarbon stream ischarged. In the practice of the present invention, such WHSV should bein the range of from about 0.5 hr.⁻¹ to about 50 hrs.⁻¹, preferably inthe range of from about 1 hr.⁻¹ to about 50 hrs.⁻¹.

[0108] Any suitable hydrocarbon stream, which comprises, consists of, orconsists essentially of sulfur containing hydrocarbons can be used asthe feed to be contacted with the inventive composition. The hydrocarbonstream preferably comprises, consists of, or consists essentially of afuel selected from the group consisting of a cracked gasoline, dieselfuel, and combinations thereof.

[0109] The amount of sulfur in the hydrocarbon stream can be in therange of from about 100 ppm sulfur by weight of the hydrocarbon streamto about 50,000 ppm. When the hydrocarbon stream is cracked gasoline,the amount of sulfur can be in the range of from about 100 ppm sulfur byweight of the cracked gasoline to about 10,000 ppm sulfur by weight ofthe cracked gasoline. When the hydrocarbon stream is diesel fuel, theamount of sulfur can be in the range of from about 100 ppm sulfur byweight of the diesel fuel to about 50,000 ppm sulfur by weight of thediesel fuel.

[0110] As used herein, the terms “sulfur” or “ppmw sulfur” denotes theamount of atomic sulfur (about 32 atomic mass units) contained in thesulfur-containing hydrocarbons of the hydrocarbon stream, based on thetotal weight of the hydrocarbon stream, not the atomic mass, or weight,of a sulfur compound, such as an organo-sulfur compound.

[0111] The cracked gasoline or diesel fuel, suitable as a feed in aprocess of the present invention, is a composition that contains, inpart, olefins, aromatics, sulfur, paraffins and naphthenes.

[0112] The amount of olefins in cracked gasoline is generally in therange of from about 10 to about 35 weight percent olefins based on thetotal weight of the cracked gasoline. For diesel fuel there isessentially no olefin content.

[0113] The amount of aromatics in cracked gasoline is generally in therange of from about 20 to about 40 weight percent aromatics based on thetotal weight of the cracked gasoline. The amount of aromatics in dieselfuel is generally in the range of from about 10 to about 90 weightpercent aromatics based on the total weight of the diesel fuel.

[0114] In carrying out the desulfurization step of a process of thepresent invention, it is preferred that the hydrocarbon stream be in agas or vapor phase. However, in the practice of the present invention,it is not essential that such hydrocarbon stream be totally in a gas orvapor phase.

[0115] In carrying out the desulfurizing step, it is presently preferredthat an agent be employed which interferes with any possible chemical orphysical reacting of the olefinic or aromatic compounds in thehydrocarbon stream which is being treated with the inventivecomposition. Preferably such agent is hydrogen.

[0116] Hydrogen flow in the desulfurization zone is generally such thatthe mole ratio of hydrogen to the hydrocarbon stream is the range offrom about 0.1 to about 10, preferably in the range of from about 0.2 toabout 3.

[0117] If desired, during the desulfurization of the cracked gasoline ordiesel fuel, diluents such as methane, carbon dioxide, flue gas,nitrogen, and the like and combinations thereof can be used. Thus, it isnot essential to the practice of the present invention that a highpurity hydrogen be employed in achieving the desired desulfurization ofthe hydrocarbon stream such as, but not limited to, cracked gasoline ordiesel fuel.

[0118] It is presently preferred when utilizing a fluidized bed reactorsystem that a composition be used having a particle size in the range offrom about 10 micrometers to about 1000 micrometers. Preferably, suchcomposition should have a particle size in the range of from about 20micrometers to about 500 micrometers, and, more preferably, in the rangeof from 30 micrometers to 400 micrometers. When a fixed bed reactorsystem is employed for the practice of a desulfurization process of thepresent invention, the composition should generally have a particle sizein the range of about {fraction (1/32)} inch to about ½ inch diameter,preferably in the range of from about {fraction (1/32)} inch to about ¼inch diameter.

[0119] It is further presently preferred to use a composition having asurface area in the range of about 1 square meter per gram (m²/g) toabout 1000 square meters per gram of composition, preferably in therange of from about 1 m²/g to about 800 m²/g.

[0120] The desulfurized hydrocarbon stream can be separated from thesulfurized composition by any appropriate separation method known in theart thereby forming a separated desulfurized hydrocarbon stream and aseparated sulfurized composition.

[0121] Examples of such means are cyclonic devices, settling chambers,impingement devices for separating solids and gases, and the like andcombinations thereof. Separation can include, but is not limited to,allowing the hydrocarbon stream to flow out of the desulfurization zone.The desulfurized gaseous cracked gasoline or desulfurized gaseous dieselfuel, can then be recovered and preferably liquefied. Liquification ofsuch desulfurized hydrocarbon streams can be accomplished by any mannerknown in the art.

[0122] The amount of sulfur in the desulfurized hydrocarbon stream,following treatment in accordance with a desulfurization process of thepresent invention, is less than about 500 ppm sulfur by weight ofhydrocarbon stream, preferably less than about 150 ppm sulfur by weightof hydrocarbon stream, and more preferably less than about 50 ppm sulfurby weight of hydrocarbon stream.

[0123] In carrying out the process of the present invention, if desired,a stripper unit can be inserted before and/or after the regeneration ofthe sulfurized composition. Such stripper will serve to remove aportion, preferably all, of any hydrocarbon from the sulfurizedcomposition. Such stripper can also serve to remove oxygen and sulfurdioxide from the system prior to the introduction of the regeneratedcomposition into the reduction zone. The stripping comprises a set ofconditions that include total pressure, temperature, and a strippingagent partial pressure.

[0124] Preferably, the total pressure in the stripper when employed isin the range of from about 25 psia to about 500 psia.

[0125] Temperature for such stripping can be in the range of from about100° F. to about 1000° F.

[0126] The stripping agent is a composition that helps to removehydrocarbon from the sulfurized composition. Preferably, the strippingagent is nitrogen. The sulfurized composition can have sulfur containedtherein (for example, within the pores of the composition) or thereon(for example, located on the surface of the composition).

[0127] The regeneration zone employs a set of conditions that includestotal pressure and sulfur removing agent partial pressure. The totalpressure is generally in the range of from about 25 psia to about 50psia.

[0128] The sulfur removing agent partial pressure is generally in therange of from about 1% to about 25% of the total pressure.

[0129] The sulfur-removing agent is a composition that helps to generategaseous sulfur containing compounds and oxygen containing compounds suchas sulfur dioxide, as well as to burn off any remaining hydrocarbondeposits that might be present. The preferred sulfur removing agentsuitable for use in the regeneration zone is selected from oxygencontaining gases such as, but not limited to, air.

[0130] The temperature in the regeneration zone is generally in therange of from about 100° F. to about 1500° F., preferably in the rangeof from about 800° F. to about 1200° F.

[0131] The regeneration zone can be any vessel wherein the desulfurizingor regeneration of the sulfurized composition can take place.

[0132] The regenerated composition is then reduced in a reduction zonewith a reducing agent including, but not limited to, hydrogen, so thatat least a portion of the promoter content of the composition is reducedto produce a reduced composition having a reduced valence promotercontent to permit the removal of sulfur from the hydrocarbon streamaccording to the inventive process disclosed herein.

[0133] In general, when practicing the present invention, reduction ofthe desulfurized composition is carried out at a temperature in therange of from about 100° F. to about 1500° F. and at a pressure in therange of from about 15 psia to about 1500 psia. Such reduction iscarried out for a time sufficient to achieve the desired level ofpromoter reduction of the promoter, which is preferably contained in theskin of the composition. Such reduction can generally be achieved in atime period in the range of from about 0.01 hour to about 20 hours.

[0134] Following the reduction of the regenerated composition, at leasta portion of the resulting reduced composition can be returned to thedesulfurization zone.

[0135] In carrying out the process of the present invention, the stepsof desulfurization, regeneration, reduction, and optionally strippingbefore and/or after such regeneration can be accomplished in the singlezone or vessel or in multiple zones or vessels.

[0136] When carrying out the process of the present invention in a fixedbed reactor system, the steps of desulfurization, regeneration,reduction, and optionally stripping before and/or after suchregeneration are accomplished in a single zone or vessel.

[0137] The desulfurized cracked gasoline can be used in the formulationof gasoline blends to provide gasoline products suitable for commercialconsumption and can also be used where a cracked gasoline containing lowlevels of sulfur is desired.

[0138] The desulfurized diesel fuel can be used in the formulation ofdiesel fuel blends to provide diesel fuel products.

EXAMPLES

[0139] The following examples are intended to be illustrative of thepresent invention and to teach one of ordinary skill in the art to makeand use the invention. These examples are not intended to limit theinvention in any way.

Example I

[0140] A ferric oxide/alumina/perlite composition was prepared. 29.4grams of ferric oxide (Fe₂O₃), 10.6 grams of Condea Disperal alumina (anacid dispersible boehmite alumina), and 12.5 grams of perlite (SibricoSil-Kleer #27-M) were added to deionized water. After mixing thoroughly,the composition was put into a muffle furnace. The temperature wasincreased 3° C. per minute to 150° C. and held there for an hour. Thetemperature was then increased to 635° C. and held there for an hour.After cooling, the sample was crushed, sized between 840 and 1700microns, and then tested.

Example II

[0141] The composition as prepared in Example I was tested for itsdesulfurization activity as follows. 10 grams of the material asprepared were placed in a ½ inch diameter quartz tube having a length ofabout 12 inches and having a glass frit positioned above the lowerone-third so as to provide an inert support for the bed of sorbent.

[0142] During each reaction cycle, the reactor was maintained at atemperature of 7500 F and a pressure of 15 pounds per square inchabsolute (psia). Hydrogen flow was at 130 standard cubic centimeters perminute (seem) diluted with 130 seem of nitrogen. Gaseouscracked-gasoline was pumped upwardly through the reactor at a rate of13.4 ml per hour. Such conditions are hereinafter referred to as“reaction conditions.”

[0143] The gaseous cracked-gasoline had a motor octane number of 80.5(MON) or 91.4 (RON) by engine tests, an olefin content of 20.4 weightpercent, 340 parts per million (ppm) sulfur by weight sulfur-compoundsbased on the total weight of the gaseous cracked-gasoline with about 95weight percent of the sulfur in the form of thiophenic compounds.

[0144] Before Cycle 1 was initiated, the composition was reduced withhydrogen flowing at a rate of 300 seem at a temperature of 750° F. for aperiod of one hour. Such conditions are hereinafter referred to as“reducing conditions.” Each reaction cycle consisted of four hours withthe product sulfur (ppm) for each cycle measured after two, three, andfour hours of exposure to the feed.

[0145] After completion of the reaction cycle, the composition wasflushed with 180 seem nitrogen at 750° F. for fifteen minutes. Thetemperature was then raised to 1000° F. where the composition wasregenerated under 120 seem air and 180 seem nitrogen for two hours. Thetemperature was then decreased to 750° F. and the sample purged withnitrogen for 15 minutes. Such conditions are hereinafter referred to as“regeneration conditions.” Cycle 2 began, like Cycle 1 under reducingconditions; i.e., with treatment at 750° F. of the sorbent in hydrogenat a flow rate 300 seem for one hour.

[0146] The composition in Example I was tested over two reaction cycleswith regeneration occurring after Cycle 1. The results in Table I wereobtained where the values given are the parts per million by weight ofsulfur in the product after the second hour, third hour, and fourth hourof treatment, respectively. TABLE I Fe₂O₃ Alone Feed - 340 ppm SulfurTime Cycle 1 (ppm S) Cycle 2 (ppm S) Second Hour 13 132 Third Hour 31179 Fourth Hour 56 172

[0147] The effect of this treatment upon octane number was determinedfrom gas chromatographic analysis of the feed and product samples. Thesemeasurements on samples taken after third hour indicate that thedesulfurization reaction caused a slight decrease in product (RON+MON)/2of 0.07 for cycle 1 and 0.17 for cycle 2.

Example III

[0148] A ferric oxide/alumina/perlite composition promoted with nickelwas prepared. 39.6 grams of nickel nitrate hexahydrate, 29.4 grams offerric oxide (Fe₂O₃), 10.6 grams of Condea Disperal alumina (an aciddispersible boehmite alumina), and 12.5 grams of perlite (SibricoSil-Kleer #27-M) were added to deionized water. After mixing thoroughly,the composition was put into a muffle furnace. The temperature wasincreased 3° C. per minute to 150° C. and held there for an hour. Thetemperature was then increased to 635° C. and held there for an hour.After cooling, the sample was crushed, sized between 840 and 1700microns, and then tested.

Example IV

[0149] 10 grams of the nickel promoted ferric oxide composition asprepared in Example III were tested for desulfurization activity asdescribed in Example II. The composition was tested over two reactioncycles with the results in Table II given in parts per million by weightof sulfur in the product after the second hour, third hour, and fourthhour of treatment, respectively. TABLE II Fe₂O₃ Promoted With NickelFeed - 340 ppm Sulfur Time Cycle 1 (ppm S) Cycle 2 (ppm S) Second Hour 711 Third Hour 23 25 Fourth Hour 35 35

[0150] The nickel promoted sorbent showed almost no change indesulfurization activity over the two cycles. The effect of thistreatment upon octane number was also determined from gaschromatographic analysis of the feed and product samples. Thesemeasurements on samples taken after third hour indicate that thedesulfurization reaction caused a slight decrease in product (RON+MON)/2of 0.36 for cycle 1 and 0.34 for cycle 2. These results demonstrate thatthese compositions give high desulfurization with small octane changes.

That which is claimed:
 1. A composition comprising: (a) an iron oxide;and (b) a promoter wherein at least a portion of said promoter ispresent as a reduced valence promoter.
 2. A composition in accordancewith claim 1 wherein said promoter is present in an amount which willeffect the removal of sulfur from a hydrocarbon stream when contactedwith said composition under desulfurization conditions.
 3. A compositionin accordance with claim 1 wherein said promoter comprises a metalselected from the group consisting of nickel, cobalt, iron, manganese,copper, zinc, molybdenum, tungsten, silver, tin, antimony, vanadium,gold, platinum, ruthenium, iridium, chromium, palladium, titanium,zirconium, rhodium, rhenium, and combinations of any two or morethereof.
 4. A composition in accordance with claim 1 wherein said ironoxide is present in an amount in the range of from about 10 to about 90weight percent.
 5. A composition in accordance with claim 1 wherein saidiron oxide is present in an amount in the range of from about 30 toabout 80 weight percent.
 6. A composition in accordance with claim 1wherein said iron oxide is present in an amount in the range of from 40to 70 weight percent.
 7. A composition in accordance with claim 1wherein said promoter is present in an amount in the range of from about1 to about 60 weight percent.
 8. A composition in accordance with claim1 wherein said promoter is present in an amount in the range of fromabout 5 to about 40 weight percent.
 9. A composition in accordance withclaim 1 wherein said promoter is present in an amount in the range offrom 8 to 20 weight percent.
 10. A composition in accordance with claim1 wherein said promoter comprises nickel.
 11. A composition inaccordance with claim 1 wherein said promoter comprises iron.
 12. Acomposition in accordance with claim 1 wherein said composition is aparticulate in the form of one of granules, extrudates, tablets,spheres, pellets, or micro spheres.
 13. A composition in accordance withclaim 12 wherein said particulate is a microsphere.
 14. A compositioncomprising: (a) an iron oxide; (b) a silicon-containing material; (c) analuminum-containing material selected from the group consisting ofalumina, aluminate, and combinations thereof; and (d) a promoter whereinat least a portion of said promoter is present as a reduced valencepromoter.
 15. A composition in accordance with claim 14 wherein saidpromoter is present in an amount which will effect the removal of sulfurfrom a hydrocarbon stream when contacted with said composition underdesulfurization conditions.
 16. A composition in accordance with claim14 wherein said promoter comprises a metal selected from the groupconsisting of nickel, cobalt, iron, manganese, copper, zinc, molybdenum,tungsten, silver, tin, antimony, vanadium, gold, platinum, ruthenium,iridium, chromium, palladium, titanium, zirconium, rhodium, rhenium, andcombinations of any two or more thereof.
 17. A composition in accordancewith claim 14 wherein said iron oxide is present in an amount in therange of from about 10 to about 90 weight percent.
 18. A composition inaccordance with claim 14 wherein said iron oxide is present in an amountin the range of from about 30 to about 80 weight percent.
 19. Acomposition in accordance with claim 14 wherein said iron oxide ispresent in an amount in the range of from 40 to 70 weight percent.
 20. Acomposition in accordance with claim 14 wherein said promoter is presentin an amount in the range of from about 1 to about 60 weight percent.21. A composition in accordance with claim 14 wherein said promoter ispresent in an amount in the range of from about 5 to about 40 weightpercent.
 22. A composition in accordance with claim 14 wherein saidpromoter is present in an amount in the range of from 8 to 20 weightpercent.
 23. A composition in accordance with claim 14 wherein saidsilicon-containing material is present in an amount in the range of fromabout 10 to about 40 weight percent and said aluminum-containingmaterial is present in an amount in the range of from about 1 to about30 weight percent.
 24. A composition in accordance with claim 14 whereinsaid silicon-containing material is present in an amount in the range offrom about 12 to about 35 weight percent and said aluminum-containingmaterial is present in an amount in the range of from about 5 to about25 weight percent.
 25. A composition in accordance with claim 14 whereinsaid silicon-containing material is present in an amount in the range offrom 15 to 30 weight percent and said aluminum-containing material ispresent in an amount in the range of from 10 to 22 weight percent.
 26. Acomposition in accordance with claim 14 wherein said promoter comprisesnickel.
 27. A composition in accordance with claim 14 wherein saidpromoter comprises iron.
 28. A composition in accordance with claim 14wherein said silicon-containing material is present in the form ofexpanded perlite.
 29. A composition in accordance with claim 28 whereinsaid expanded perlite is milled.
 30. A composition in accordance withclaim 14 wherein said composition is a particulate in the form of one ofgranules, extrudates, tablets, spheres, pellets, or miscrospheres.
 31. Acomposition in accordance with claim 30 wherein said particulate is amicrosphere.
 32. A process for the production of a compositioncomprising: (a) admixing: 1) a liquid, 2) an iron-containing compound,3) a silicon-containing material, 4) alumina, and 5) a promoter so as toform a mixture thereof; (b) drying said mixture so as to form a driedmixture; (c) calcining said dried mixture so as to form a calcinedmixture; (d) reducing said calcined mixture with a suitable reducingagent under suitable conditions to produce a composition having areduced valence promoter content therein, and (e) recovering saidcomposition.
 33. A process in accordance with claim 32 wherein saidcalcined mixture is reduced in step (d) such that said composition willeffect the removal of sulfur from a stream of hydrocarbons when suchstream is contacted with same under desulfurization conditions.
 34. Aprocess in accordance with claim 32 wherein said promoter comprises ametal selected from the group consisting of nickel, cobalt, iron,manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony,vanadium, gold, platinum, ruthenium, iridium, chromium, palladium,titanium, zirconium, rhodium, rhenium, and combinations of any two ormore thereof.
 35. A process in accordance with claim 32 wherein saidsilicon-containing material is in the form of expanded perlite.
 36. Aprocess in accordance with claim 32 wherein said mixture from step (a)is in the form of one of a wet mix, dough, paste, or slurry.
 37. Aprocess in accordance with claim 32 wherein said mixture from step (a)is particulated prior to said drying in step (b).
 38. A process inaccordance with claim 32 wherein said mixture from step (a) isparticulated in the form of one of granules, extrudates, tablets,spheres, pellets, or microspheres prior to said drying in step (b). 39.A process in accordance with claim 32 wherein said mixture from step (a)is particulated by spray drying in step (b) so as to form said driedmixture.
 40. A process in accordance with claim 32 wherein said mixtureis dried in step (b) at a temperature in the range of from about 150° F.to about 450° F.
 41. A process in accordance with claim 32 wherein saiddried mixture is calcined in step (c) at a temperature in the range offrom about 400 to about 1500° F.
 42. A process in accordance with claim32 wherein said composition recovered in step (e) comprises: (a) an ironoxide; (b) said silicon-containing material; (c) an aluminum-containingmaterial selected from the group consisting of alumina, aluminate andcombinations thereof, and (d) a promoter wherein at least a portion ofsaid promoter is present as a reduced valence promoter.
 43. A process inaccordance with claim 42 wherein said iron oxide is present in an amountin the range of from about 10 to about 90 weight percent.
 44. A processin accordance with claim 42 wherein said iron oxide is present in anamount in the range of from about 30 to about 80 weight percent.
 45. Aprocess in accordance with claim 42 wherein said iron oxide is presentin an amount in the range of from 40 to 70 weight percent.
 46. A processin accordance with claim 42 wherein said promoter is present in anamount in the range of from about 1 to about 60 weight percent.
 47. Aprocess in accordance with claim 42 wherein said promoter is present inan amount in the range of from about 5 to about 40 weight percent.
 48. Aprocess in accordance with claim 42 wherein said promoter is present inan amount in the range of from 8 to 20 weight percent.
 49. A process inaccordance with claim 42 wherein said silicon-containing material ispresent in an amount in the range of from about 10 to about 40 weightpercent and said aluminum-containing material is present in an amount inthe range of from about 1 to about 30 weight percent.
 50. A process inaccordance with claim 42 wherein said silicon-containing material ispresent in an amount in the range of from about 12 to about 35 weightpercent and said aluminum-containing material is present in an amount inthe range of from about 5 to about 25 weight percent.
 51. A process inaccordance with claim 42 wherein said silicon-containing material ispresent in an amount in the range of from 15 to 30 weight percent andsaid aluminum-containing material is present in an amount in the rangeof from 10 to 22 weight percent.
 52. A process in accordance with claim32 wherein said promoter is comprised of nickel.
 53. A process inaccordance with claim 32 wherein said promoter is comprised of iron. 54.A process in accordance with claim 32 wherein said calcined mixture isreduced in step (d) at a temperature in the range of from about 100° F.to about 1500° F. and at a pressure in the range of from about 15 toabout 1500 psia and for a time sufficient to permit the formation of areduced valence promoter.
 55. A process in accordance with claim 32wherein during said calcining of step (c) at least a portion of saidalumina is converted to aluminate.
 56. A composition prepared by theprocess of claim
 32. 57. A composition prepared by the process of claim37.
 58. A composition prepared by the process of claim
 43. 59. Acomposition prepared by the process of claim
 44. 60. A compositionprepared by the process of claim
 46. 61. A composition prepared by theprocess of claim
 47. 62. A composition prepared by the process of claim49.
 63. A process for the production of a composition comprising: (a)admixing: 1) a liquid, 2) an iron-containing compound, 3) asilicon-containing material, and 4) alumina so as to form a mixturethereof; (b) drying said mixture so as to form a dried mixture; (c)calcining said dried mixture so as to form a calcined mixture; (d)incorporating a promoter onto or into said calcined mixture so as toform a promoted mixture; (e) drying said promoted mixture so as to forma dried promoted mixture; (f) calcining said dried promoted mixture soas to form a calcined promoted mixture; (g) reducing said calcinedpromoted mixture with a suitable reducing agent under suitableconditions to produce a composition having a reduced valence promotercontent therein; and (h) recovering said composition.
 64. A process inaccordance with claim 63 wherein said calcined promoted mixture isreduced in step (g) such that said composition of step (g) will effectthe removal of sulfur from a stream of hydrocarbons when such stream iscontacted with same under desulfurization conditions.
 65. A process inaccordance with claim 63 wherein said calcined mixture from step (c) isincorporated with a promoter comprised of at least one metal selectedfrom the group consisting of nickel, cobalt, iron, manganese, copper,zinc, molybdenum, tungsten, silver, tin, antimony, vanadium, gold,platinum, ruthenium, iridium, chromium, palladium, titanium, zirconium,rhodium, rhenium, and combinations of any two or more thereof.
 66. Aprocess in accordance with claim 63 wherein said silicon-containingmaterial is present in the form of expanded perlite.
 67. A process inaccordance with claim 63 wherein said mixture from step (a) is in theform of one of a wet mix, dough, paste, or slurry.
 68. A process inaccordance with claim 63 wherein said mixture from step (a) isparticulated prior to drying in step (b).
 69. A process in accordancewith claim 63 wherein said mixture from step (a) is particulated in theform of one of granules, extrudates, tablets, spheres, pellets, ormicrospheres.
 70. A process in accordance with claim 63 wherein saidmixture from step (a) is particulated by spray drying in step (b) so asto form said dried mixture.
 71. A process in accordance with claim 63wherein said mixture and said promoted mixture are each dried in steps(b) and (e), respectively, at a temperature in the range of about 150°F. to about 450° F.
 72. A process in accordance with claim 63 whereinsaid dried mixture and said dried promoted mixture are each calcined insteps (c) and (f), respectively, at a temperature in the range of about400 to about 1500° F.
 73. A process in accordance with claim 63 whereinsaid composition recovered in step (h) comprises: (a) an iron oxide; (b)said silicon-containing material; (c) an aluminum-containing materialselected from the group consisting of alumina, aluminate andcombinations thereof; and (d) a promoter wherein at least a portion ofsaid promoter is present as a reduced valence promoter.
 74. A process inaccordance with claim 73 wherein said iron oxide is present in an amountin the range of from about 10 to about 90 weight percent.
 75. A processin accordance with claim 73 wherein said iron oxide is present in anamount in the range of from about 30 to about 80 weight percent.
 76. Aprocess in accordance with claim 73 wherein said iron oxide is presentin an amount in the range of from about 40 to about 70 weight percent.77. A process in accordance with claim 73 wherein said promoter ispresent in an amount in the range of from about 1 to about 60 weightpercent.
 78. A process in accordance with claim 73 wherein and saidpromoter is present in an amount in the range of from about 5 to about40 weight percent.
 79. A process in accordance with claim 73 whereinsaid promoter is present in an amount in the range of from 8 to 20weight percent.
 80. A process in accordance with claim 73 wherein saidsilicon-containing material is present in an amount in the range of fromabout 10 to about 40 weight percent and said aluminum-containingmaterial is present in an amount in the range of from about 1.0 to about30 weight percent.
 81. A process in accordance with claim 73 whereinsaid silicon-containing material is present in an amount in the range offrom about 12 to about 35 weight percent and said aluminum-containingmaterial is present in an amount in the range of from about 5 to about25 weight percent.
 82. A process in accordance with claim 63 whereinsaid silicon-containing material is present in an amount in the range offrom 15 to 30 weight percent and said alumina is present in an amount inthe range of from 10 to 22 weight percent.
 83. A process in accordancewith claim 63 wherein said promoter is comprised of nickel.
 84. Aprocess in accordance with claim 63 wherein said promoter is comprisedof iron.
 85. A process in accordance with claim 63 wherein the reductionof said calcined promoted mixture in step (g) is carried out at atemperature in the range of from about 100° F. to about 1500° F. and ata pressure in the range of from about 15 to about 1500 psia and for atime sufficient to permit the formation of a reduced valence promoter.86. A process in accordance with claim 63 wherein during said calciningin step (c) at least a portion of said alumina is converted toaluminate.
 87. A composition prepared by the process of claim
 63. 88. Acomposition prepared by the process of claim
 68. 89. A compositionprepared by the process of claim
 74. 90. A composition prepared by theprocess of claim
 75. 91. A composition prepared by the process of claim77.
 92. A composition prepared by the process of claim
 78. 93. Acomposition prepared by the process of claim
 80. 94. A process for theremoval of sulfur from a hydrocarbon stream comprising: (a) contactingsaid hydrocarbon stream with a composition comprising an iron oxide anda promoter wherein at least a portion of said promoter is present as areduced valence promoter and in an amount which will effect the removalof sulfur from said hydrocarbon stream in a desulfurization zone underconditions such that there is formed a desulfurized hydrocarbon streamand a sulfurized composition; (b) separating said desulfurizedhydrocarbon stream from said sulfurized composition thereby forming aseparated desulfurized hydrocarbon stream and a separated sulfurizedcomposition; (c) regenerating at least a portion of said separatedsulfurized composition in a regeneration zone so as to remove at least aportion of the sulfur contained therein and/or thereon thereby forming aregenerated composition; (d) reducing said regenerated composition in areduction zone so as to provide a reduced composition having a reducedvalence promoter content therein which will effect the removal of sulfurfrom a hydrocarbon stream when contacted with same; and thereafter (e)returning at least a portion of said reduced composition to saiddesulfurization zone.
 95. A process in accordance with claim 94 whereinsaid hydrocarbon stream comprises a fuel selected from the groupconsisting of cracked-gasoline, diesel fuel, and combinations thereof.96. A process in accordance with claim 94 wherein said desulfurizationin step (a) is carried out at a temperature in the range of from about100° F. to about 1000° F. and a pressure in the range of from about 15to about 1500 psia for a time sufficient to effect the removal of sulfurfrom said stream.
 97. A process in accordance with claim 94 wherein saidregeneration in step (c) is carried out at a temperature in the range offrom about 100° F. to about 1500° F. and a pressure in the range of fromabout 10 to about 1500 psia for a time sufficient to effect the removalof at least a portion of the sulfur from said separated sulfurizedcomposition.
 98. A process in accordance with claim 94 wherein air ispresent in step (c) as a regeneration agent in said regeneration zone.99. A process in accordance with claim 94 wherein said regeneratedcomposition from step (c) is subjected to reduction with hydrogen instep (d) in said reduction zone which is maintained at a temperature inthe range of from about 100° F. to about 1500° F. and at a pressure inthe range of from about 15 to about 1500 psia and for a period of timesufficient to effect a reduction of the valence of the promoter contentof said regenerated composition.
 100. A process in accordance with claim94 wherein said separated sulfurized composition from step (b) isstripped prior to introduction into said regeneration zone in step (c).101. A process in accordance with claim 94 wherein said regeneratedcomposition from step (c) is stripped prior to introduction to saidreduction zone in step (d).
 102. The cracked-gasoline product of theprocess of claim
 94. 103. The diesel fuel product of the process ofclaim
 94. 104. A process for the removal of sulfur from a hydrocarbonstream comprising: (a) contacting said hydrocarbon stream with acomposition comprising an iron oxide, a silicon-containing material, analuminum-containing material selected from the group consisting ofalumina, aluminate, and combinations thereof, and a promoter wherein atleast a portion of said promoter is present as a reduced valencepromoter and in an amount which will effect the removal of sulfur fromsaid hydrocarbon stream in a desulfurization zone under conditions suchthat there is formed a desulfurized hydrocarbon stream and a sulfurizedcomposition; (b) separating said desulfurized hydrocarbon stream fromsaid sulfurized composition thereby forming a separated desulfurizedhydrocarbon stream and a separated sulfurized composition; (c)regenerating at least a portion of said separated sulfurized compositionin a regeneration zone so as to remove at least a portion of the sulfurcontained therein and/or thereon thereby forming a regeneratedcomposition; (d) reducing said regenerated composition in a reductionzone so as to provide a reduced composition having a reduced valencepromoter content therein which will effect the removal of sulfur from ahydrocarbon stream when contacted with same; and thereafter (e)returning at least a portion of said reduced composition to saiddesulfurization zone.
 105. A process in accordance with claim 104wherein said hydrocarbon stream comprises a fuel selected from the groupconsisting of cracked-gasoline, diesel fuel, and combinations thereof.106. A process in accordance with claim 104 wherein said desulfurizationin step (a) is carried out at a temperature in the range of from about100° F. to about 1000° F. and a pressure in the range of from about 15to about 1500 psia for a time sufficient to effect the removal of sulfurfrom said stream.
 107. A process in accordance with claim 104 whereinsaid regeneration in step (c) is carried out at a temperature in therange of from about 100° F. to about 1500° F. and a pressure in therange of from about 10 to about 1500 psia for a time sufficient toeffect the removal of at least a portion of the sulfur from saidseparated sulfurized composition.
 108. A process in accordance withclaim 104 wherein air is present in step (c) as a regeneration agent insaid regeneration zone.
 109. A process in accordance with claim 104wherein said regenerated composition from step (c) is subjected toreduction with hydrogen in step (d) in said reduction zone which ismaintained at a temperature in the range of from about 100° F. to about1500° F. and at a pressure in the range of from about 15 to about 1500psia and for a period of time sufficient to effect a reduction of thevalence of the promoter content of said regenerated composition.
 110. Aprocess in accordance with claim 104 wherein said separated sulfurizedcomposition from step (b) is stripped prior to introduction into saidregeneration zone in step (c).
 111. A process in accordance with claim104 wherein said regenerated composition from step (c) is stripped priorto introduction to said reduction zone in step (d).
 112. Thecracked-gasoline product of the process of claim
 104. 113. The dieselfuel product of the process of claim 104.